Metallizing azoic dyeings



United States Patent Ofiee 3,061,397 Patented Oct. 30,1962

poration of Delaware N Drawing. Filed June 14, 1957, Ser. No. 665,670 6Claims. (Cl. 8-42) This invention relates to an improved process ofmetallizing azoic dyeings without the precipitation of free metal on thefibre and dyeing apparatus and at the same time yielding brighter andmore desirable shades.

It is known that fibres may be impregnated with a coupling component andpassed into a solution which contains an active diazo, either in theform of a freshly prepared diazo or as a Fast Color Salt solution underconditions suitable for coupling. Fast Color Salts are diazo compoundswhich, except for a few diazos which are sufficiently stable per se, arediazo compounds which are stabilized by salt formation such as withcertain metallic salts, e.g. MgCl ZnCl SnCl etc., arylsulfonic acidssuch as naphthalene-1,S-disulfonic acid andnaphthalene-1,3,6-trisulfonic acid, and also borofluoric acid.

One of the outstanding advantages of azoic dyeings is their fastness incontrast to that of the usual azo dyes. The fastness of azoic dyeingshas recently been improved by metallizing, i.e. by treating thepreviously dyed fibres with various metallizing agents such as Cu, Co,Cr, Ni and the like. In the art as now practiced, it is necessary to dyethe fibrous material with an azoic dye devoid of solubilizing groupsfollowed by an after treatment with a metallizing agent. The metallizingstep represents an extra step and also requires at least 20 minutes. Toovercome this, satisfactory metallization of azoic dyeings is achievedby incorporating the metallizing agent in the soaping bath as taught inmy United States application Serial No. 316,305, filed on October 22,1952 (now US. Patent 2,768,053, issued October 23, 1956).

In my United States patent application Serial No. 601,- 658, filed onAugust 2, 1956, for Method of Metallizing Azoic Dyeings (now US. Patent2,867,494, issued January 5, 1959), I disclose and claim a novel processWhereby the azoic color formation is carried out in the presence of themetallizing agent. By this process fibrous material dyed with an azoicdye, free from solubilizing groups and capable of conversion into acomplex metal compound, is endowed with improved light-, washandchlorine-fastness properties and of improved shade. In this process themetallizing agent may be dissolved in a naphtholating bath, the fibrousmaterial impregnated with this bath, usually followed by drying, and theimpregnated fibre padded or printed with an active diazo which includesa freshly prepared diazo or a diazo stabilized as a Fast Color Salt, andthen rnetallizing with hot water or preferably with steam. Thetemperature and moisture condi tions of the hot water or steam aresufliciently drastic to yield complete metallization together with colorde velopment, even when exposed to steam for less than 1 minute. Theimportant advantage of this improved method is that a satisfactory.metallized product is obtained without any additional operations otherthan the usual dyeing steps. By this procedure, economical dyeings areobtained as contrasted with the present method of after metallizingwhich requires additional steps, over and above the dyeing steps, i.e.,treatment with the metallizing agent and heating.

Despite the fact that economical dyeings having desirablecharacteristics are obtained, the latter process nevertheless lacks onefactor which is highly desirable in the dye trade. In conductingnumerous experiments with the process described in my patent, US.2,867,494, I found that under certain conditions, free copper isprecipitated. The precipitation may be on the fibre, causing splotchydyeings, or in the dyeing apparatus, such as glass, wood, etc. (parts ofwhich contain steel or iron), and the usual stainless steel, etc.resulting in a metal plating problem. The precipitation is believed tobe due to the presence of certain impurities or by-products which arereadily oxidizable and in oxidation cause a reduction of the looselycoordinated copper salt to free copper. Cleaning ofi deposit-ed copperfrom equipment is difficult in addition to the poor, uneven dyeingsresulting therefrom.

In my United States patent application Serial No. 631,- 062, filed onDecember 28, 1956, for Method of Metallizing Azoic Dyeings, now PatentNo. 2,893,814, I disclose and claim a novel process whereby theprecipitation of free metal on the fibre and dyeing apparatus is veryreadily and economically remedied by the addition of an inorganic ororganic oxidizing agent to the metallizing solution. The metallizingsolution and other details with regard to the diazo and couplingcomponents employed in azoic dyeings are fully described in myaforementioned patent application (Serial No. 601,658), the disclosureof which is incorporated herein by reference thereto. The inorganic andorganic oxidizing agents which I have found particularly useful includeall of those which are soluble in alkaline aqueous solution, and aresufficiently stable to withstand the temperature of padding which rangesfrom room temperature to 212 F., and will not destroy the diazocomponents. The disclosure of my application Serial No. 631,062 containsillustrative examples not only of the various inorganic and organicoxidizing agents but also complete details of avoiding precipitation ofthe free metal during metallizing azoic dyeings. Accordingly therefore,all such illustrations and working examples are incorporated herein byreference thereto.

I have found that the process disclosed in my pending application SerialNo. 631,062 is surprisingly improved by yielding brighter and moredesirable shades during the dyeing-metallization step by the presence of1% to 30%, based on the dye solution, of a sulfonated vegetable oil, aphenylphenol, such as for example, 0-, mand p-phenylphenols or theiralkali metal salts, and a mixture of the sulfonated vegetable oil andphenylphenol or its alkali metal salt. The sulfonated vegetable oil orthe phenylphenol or its alkali metal salt or a mixture of the two can beadded to the solution or paste at any time during the process so long asit is present during the dyeing-metallization step.

The sulfonated vegetable oils which may be employed include sulfonatedoils obtained from any non-drying and semi-drying vegetable oils having(prior to sulfonation) an iodine number ranging from 48 to 160. Asexamples of such oils which are readily sulfonated and utilized inaccordance with the present invention, the following are illustrative:oastor oil, cashew nut oil, olive oil, palm oil, peanut oil, pecan nutoil, corn oil, cottonseed oil, mustardseed oil, pine nut oil, sesameseed oil, sunflower seed oil and the like. The method of sulfonatingthese oils is well known to those skilled in the art and need not berepeated herein. Any one of the conventional sulfonating methods may beemployed to yield sulfonated vegetable oils which would be useful forthe purpose of the present invention.

In experimenting with all of the above sulfonated vegetable oils, I havefound that sulfonated castor oil, commercially available under the brandname of Monopol oil, is unique since when added to the solution or pasteat any, time during the process yields much brighter and more desirableshades than the other sulfonated vegetable oils, the alkali metal saltsof the phenylphenols and mixtures of such phenylphenols with sulfonatedvegetable oils. This uniqueness may be attributable to the fact that thesulfonated castor oil is partially sulfonated and partially sulfated.The ricinoleic acid derived from castor oil contains both an unsaturatedbond and a hydroxy group and for this reason on sulfonation yields afinal product which is partially sulfonated and partially sulfated.

The alkali metal salts of the phenylphenols include sodium and potassiummand p-phenolates. The phenylphenols and their alkali metal salts arealso well known to those skilled in the art and are commerciallyavailable under various trade and brand names.

In practicing the present invention, a Rapidogen solution is firstprepared which normally comprises about 10 parts of a Naphthol type ofcoupling component and an approximately equivalent part of an azoic typeof amine (free from solubilizing groups such as sulfonic and carboxylicacid groups) diazotized and stabilized with a primary or secondary aminetogether with a sufficient amount of caustic to dissolve the Naphthol, 5to 30 parts of an alkaline glycol type solvent and 70-130 parts ofwater. The alkaline glycol solvents that may be employed includeethylene glycol, diethylene glycol, propylene glycol, glycol monomethylether, glycol monoethyl ether, glycol monobutyl ether. Preferably amixture of a glycol, e.g. glycol and diethylene glycol and a glycolmonoether, e.g. Cellosolve, is employed. To this is then added l-30% ofa sulfonated vegetable oil, an alkali metal salt of phenylphenol or amixture of the two based on the weight of the dye solution.

To the dye solution is then added 0.1- parts of a copper salt which waspreviously dissolved and coordinated. As examples of such coordinatingor chelating agents, the following are illustrative: triethanolamine,tartaric acid, glycine, dimethylglycine, glycollic acid, aspartic acid,glutamic acid, lactic acid, a-hydroxy-butyric acid and the like. Theamount of chelating agent employed is that necessary to maintainsolubility of the metal salt under alkaline conditions and may rangefrom 5-25 parts of chelating agent per 10 parts by weight of metal salt.Theoretically, the chelating agents are added in approximatelyequivalent amounts to that of the metallizing compound, but in actualpractice the aforementioned proportions may be departed from to obtainthe most desirable results depending on conditions of dyeing and type ofcoordinating agent employed. Approximately one mole of copper to two ofdye gives satisfactory improvement, although frequently the ratio ofcopper to dye is much less, i.e. as low as 0.1 mole of copper to 2 molesof dye.

The solution as above prepared may contain 1020% of an oxidizing agent,as disclosed in the aforementioned application Serial -No. 631,062,based on the weight of the metallizing agent.

The following examples will illustrate the preferred embodiments of thepresent invention. It is to be clearly understood that these examplesare illustrative and are not to be considered as limitative. All partsgiven are by weight unless otherwise stated.

EXAMPLE I A metallizing solution containing an oxidizing agent wasprepared as follows:

Copper Solution .3 part of cupric chloride crystals .35 part oftriethanolamine .18 part of caustic soda (dry) 2.0 parts of water Afterformation of a blue solution, 0.3 part of sodium chromate anhydrous wasadded.

A concentrated solution Was prepared from 120 parts of a commerciallyavailable Rapidogen Blue GN solu- 4 tion consisting of 11 parts oftetrazotized and stabilized o-dianisidine, i.e. stabilized with methyltaurine, 10 parts of 3-hydroXy-2-naphthanilide, 6 parts of sodiumhydroxide 71 parts of combined water and solvent consisting of 7 partsof diethylene glycol, 10 parts of Cellosolve and 54 parts of water.

To 12 parts of the above concentrated solution, 3.13 parts of the abovecopper solution was added with stirring and 2 parts of sulfonated castoroil, commercially available under the brand name of Monopol oil, wasadded. The resulting solution was thickened with 70 parts of starchtragacanth and adjusted with 12.87 parts of water to yield a printingpaste.

A 10 gram sample of cotton was printed with the paste, steamed in acidsteam in a normal manner for 2 minutes, rinsed and dried. A very brightblue shade obtained was much brighter and greener in color than asimilar dyeing obtained with a printing paste containing no sulfonatedcastor oil.

EXAMPLE II Example I was repeated with the exception that .3 part ofcupric chloride crystals was replaced by .45 part of copper sulfate. Theresults obtained were identical.

EXAMPLE III Example I was again repeated with the exception that 2 partsof sulfonated castor oil were replaced by 2 parts of sodiump-phenylphenolate. The results obtained were identical with those ofExample I.

EXAMPLE IV Example I was repeated with the exception that 2 parts ofsulfonated castor oil were replaced by 2 parts of sodiumo-phenylphenolate. The results obtained were identical with those ofExample 1.

EXAMPLE V Example I was again repeated with the exception that 2 partsof sulfonated castor oil were replaced by a mixture consisting of 1 partof sulfonated castor oil and 1 part of sodium p-phenylphenolate. Theresults obtained were similar as in the previous examples with theexception that in this case the dyeings were a little brighter andgreener.

EXAMPLE VI Example I was again repeated with the exception that 2 partsof sulfonated castor oil were replaced by a mixture consisting of 1 partof sulfonated corn oil and 1 part of sodium o-phenylphenolate. Theresults were similar to but a little brighter and greener than thoseobtained in Examples I to IV inclusive.

EXAMPLE VII Example I was again repeated with the exception that 2 partsof sulfonated castor oil were replaced by 0.5 part of sodiump-phenylphenolate.

EXAMPLE VIII A metallizing solution containing an oxidizing agent wasprepared as follows:

Copper Solution 147 grams of copper sulfate 643 grams of water grams oftriethanolamine 60 grams of caustic soda (dry) After formation of a bluesolution, 40 grams of sodium chromate anhydrous was added.

A padding solution was prepared by mixing the following components:

3 grams of Naphthol AS (3-hydroxy-2-naphthanilide) 6 cc. of ethylalcohol 1.5 cc. of caustic soda 34 B.

1.5 grams of sulfonated castor oil The padding solution was poured intocc. of the above copper solution together with 2.5 cc. of caustic soda34 B. and water to yield a total volume of 133 cc.

A 10' gram sample of muslin was padded with the above solution, driedand padded with a solution consisting of:

7 grams of o-dianisidine which had been stabilized with zinc chloride .5cc. of Diazopon AN (fatty alcohol-ethylene oxide con densation productused as a protective colloid), and

2 cc. of acetic acid 50% aqueous solution Sufficient water was added togive a total volume of 133 tetrazotized and The padding was carried outon a 3-roll padder consisting of rubber rolls and stainless steel padbase.

The muslin was skyed (passed through the atmosphere) for a few secondsand then aged in neutral steam at atmospheric pressure for seconds. Adeep, rich blue coloration was obtained having excellent wash-, lightandchlorine-fastness without the minutest evidence of copper precipitation.

EXAMPLE IX Example VIII was repeated 7 times. In the first exampleidentified as A no sulfonated vegetable oil or phenylphenols or theiralkali metal salts were added to the padding solution. In repeatexamples B to G inclusive, 1.5 grams of sulfonated castor oil of ExampleVIII were replaced by B, a mixture consisting of 1 gram of sulfonatedcastor oil and 1 gram of sodium o-phenylphenolate; C, 1.5 grams ofpotassium p-phenylphenolate; D, 1.5 grams of sodium p-phenylphenolate;E, 1.5 grams of potassium o-phenylphenolate; F, 1.5 grams of sodiumo-phenylphenolate; and G, 1.5 grams of sulfonated castor oil,respectively.

The repeat example A, i.e. containing no sulfonated vegetable oil orphenylphenol or its alkali metal salt, after color development, gave adeep, rich blue coloration having excellent wash-, lightandchlorine-fastness without any evidence of copper precipitation. Therepeat examples C to G gave more desirable brighter and greenercolorations and shades whereas repeat example B showed a considerableimprovement, i.e. much brighter and greener over repeat examples C to Ginclusive.

EXAMPLE X Example VIII was repeated with the exception that the NaphtholAS in the padding solution was replaced by 2 grams of phenylmethylpyrazolone and 1.5 grams of sulfonated castor oil were replaced by 1.5grams of sodium p-phenylphenolate. A tan coloration was produced whichwas very much brighter than the dyeing in which the padding soluioncontained no sodium p-phenylphenolate.

EXAMPLE )G Example VIII was again repeated with the exception that theNaphthol AS was replaced by an equivalent amount of Z-hydroxybenzene-azo-4-resorcinol and the o-dianisidine tetrazotized andstabilized with zinc chloride, was replaced by an equivalent amount ofzinc chloride double salt of diazotized S-chloro-o-anisidine. A browndyeing was obtained which showed excellent light-, washandchlorine-fastness with no precipitation of metallic copper on the fibreor in the padding solution. The shade was very much brighter andstronger than the dyeing without sulfonated castor oil in the paddingsolution.

EXAMPLE XII Example VIII was again repeated with the exception that theNaphthol AS in the repeated padding solution was replaced by anequivalent amount of 3-hydroxy-2- naphthoic acid o-toluidide and theo-dianisidine, tetrazotized and stabilized with zinc chloride, wasreplaced by an equivalent amount of zinc chloride double salt of thediazo from 5-n-butylsulfamyl-oranisidine. 1 gram ofsodium-p-phenylphenolate was added to the padding solution. After colordevelopment, a real dyeing of improved properties was obtained whichshowed excellent light-, washand chlorine-fastness with no evidencewhatsoever of copper precipitation on the fibre or in the paddingsolution.

EXAMPLE XIII Example VIII was repeated with the exception that thesulfonated castor oil was replaced by 1.5 grams of sodiumo-phenylphenolate and the copper solution was replaced by the followingcopper solution:

grams of glycine 400 grams of water 100 grams of copper chloride 300 cc.of caustic soda 34 B. 100 grams of sodium perborate After colordevelopment, a much greener shade of blue was obtained than with asimilar dyeing without the presence of sodium o-phenylphenolate in thepadding solution.

EXAMPLE XIV Example VIII was again repeated with the exception that thecopper solution was replaced by the following copper solution:

100 grams of glutamic acid 400 grams of water 100 grams of coppersulfate 300 grams of caustic soda 34 B.

100 grams of m-nitrobenzenesulfonic acid sodium salt A much brighter,greener shade of blue was obtained after color development than when adyeing was made in identical manner without the presence of sulfonatedcastor oil.

EXAMPLE XV Example I was repeated with the exception that 2 grams ofsulfonated castor oil were replaced by 2 grams of sulfonated cottonseedoil in the Rapidogen solution. A much brighter and greener shade of bluewas obtained than in a similar dyeing without the presence of thesulfonated cottonseed oil in the concentrated Rapidogen solution.

EXAMPLE XVI A printing paste was prepared as follows:

4 grams of a Rapidogen mix, consisting of equivalent amounts ofcresidine diazotized and stabilized with sarcosine, and3-hydroxy-3'-nitro-2-naphthanilide, 4 cc. of ethylene glycol monoethylether, 24 cc. of water, 3 cc. of sodium hydroxide 34 B. and 5 cc. ofcopper solution of Example I were combined and 70 grams of gumtragacanth added to printing thickness. To the printing paste were added1.5 grams of sodium o-phenylphenolate.

A 10 gram sample of cotton cloth was printed with the above paste anddeveloped for 2 minutes in acidified steam. The Bordeaux print showedvery excellent light-, washand chlorine-fastness with no evidence ofmetallic copper on the printed cotton fibre.

EXAMPLE XVII Example XVI was repeated with the exception that 4 grams ofthe Rapidogen mix was replaced by 4 grams of a Rapidogen mix consistingof an equivalent amount of o-dianisidine tetrazotized and stabilizedwith methyl taurine and phenyl methyl pyrazolone, and 10 cc. of thecopper solution of Example VIII together with 1.5 grams of sulfonatedpeanut oil. A very bright tan shade was produced, after colordevelopment, having excellent light-, washand chlorine-fastness with noevidence of metallic copper on the printed cotton fibre.

7 EXAMPLE XVIII Example XVI was again repeated with the exception that 4grams of the Rapidogen mix was replaced by 4 grams of a Rapidogen mixconsisting of an equivalent amount of4-benzoylamino-Z-methoxy-S-methylaniline diazotized and stabilized withsarcosine and Naphthol AS, together with a mixture consisting of 1 gramof sulfonated cottonseed oil and 2 grams of sodium o-phenylphenolate.After color development, a very bright violet print was obtained whichshowed excellent light-, washand chlorine-fastness with no evidence ofmetallic copper on the printed fibre.

I claim:

1. The process of producing metallized azoic prints and dyeings in situwhich comprises treating a fibrous material with an azoic couplingcomponent which is free from solubilizing group and a diazo componentderived from an amine base free from solubilizing groups and which bothazoic dye components are capable of yielding an o,o-dihydroxy azoconfiguration, followed by a treatment at elevated temperatures in thepresence of a coordinating agent selected from the class consisting oflower alkylolamines and aliphatic aminoand hydroxy-carboxylic acids, anda metallizing copper compound from the class consisting of soluble anddispersible salts and hydroxides of copper, and an oxidizing agentequivalent to 10100% based on the weight of the metallizing agent,selected from the class consisting of alkali perborates, alkalichromates, hydrogen peroxide, alkali peroxides and nitrobenzenesultonicacids and their alkali salts, and in the presence of a compound selectedfrom the class consisting of o-, m-, and p-phenylphenols and the alkalimetal salts thereof in an amount ranging from 1% to 30% based on theweight of the dye solution.

2. The process according to claim 1 wherein the compound is sodiumo-phenylphenolate.

3. The process according to claim 1 wherein the compound is sodiump-phenylphenolate.

4. A composition of matter for use in azoic dye manufacture whichcomprises a dye solution of an azoic coupling component free fromsolubilizing groups, a diazoamino compound derived from an amine basefree from solubilizing groups which has been diazotized and stabilizedwith a primary and secondary amine containing at least one solubilizinggroup, said azoic dye components yielding an o,o'-dihydroxy azo dyeconfiguration in the final dye, a coordinating agent selected from theclass consisting of lower alkylolamines and aliphatic aminoandhydroxy-carboxylic acids, a metallizing copper compound from the classconsisting of soluble and dispersible salts of hydroxides of copper, anoxidizing agent equivalent to 10-100% based on the weight of themetallizing agent selected from the class consisting of alkaliperborates, alkali chromates, hydrogen peroxide, alkali peroxides andnitrobenzenesulfonic acids and their alkali salts, and a phenylphenolcompound selected from the class consisting of 0-, mand p-phenylphenolsand the alkali metal salts thereof in an amount ranging from 1% to 30%based on the weight of the dye solution.

5. A composition of matter according to claim 4 wherein the phenylphenolcompound is sodium o-phenylphenolate.

6. A composition of matter according to claim 4 wherein the phenylphenolcompound is sodium p-phenylphenolate.

References Cited in the file of this patent UNITED STATES PATENTS569,392 Storck Oct. 13, 1896 2,029,568 Jaeck Feb. 4, 1936 2,867,494Streck J an. 6, 1959 2,893,814 Streck July 7, 1959 FOREIGN PATENTS502,144 Great Britain Mar. 7, 1939 531,470 Great Britain I an. 6, 194165,232 Norway Sept. 21, 1942 OTHER REFERENCES Diserens: Chemical Tech.of Dyeing and Printing, vol. 1, page 320.

1. THE PROCESS OF PRODUCING METALLIZED AZOIC PRINTS AND DYEINGS IN SITUWHICH COMPRISES TREATING A FIBROUS MATERIAL WITH AN AZOIC COUPLINGCOMPONENT WHICH IS FREE FROM SOLUBILIZING GROUPS AND A DIAZO COMPONENTDERIVED FROM AN AMINE BASE FREE FROM SOLUBILIZING GROUPS AND WHICH BOTHAZOIC DYE COMPONENTS ARE CAPABLE OF YEILDING AN O,O''-DIHYDROXY AZOCONFIGURATION, FOLLOWED BY A TREATMENT AT ELEVATED TEMPERATURES IN THEPRESENCE OF A COORDINATING AGENT SELECTED FROM THE CLASS CONSISTING OFLOWER ALKYLOLAMINES AND ALIPHATIC AMINO- AND HYDROXY-CARBOXYLIC ACIDS,AND A METALLIZING COPPER COMPOUND FROM THE CLASS CONSISTING OF SOLUBLEAND DISPERSIBLE SALTS AND HYDROXIDES OF COPPER, AND AN OXIDIZING AGENTEQUIVALENT TO 10-100% BASED ON THE WEIGHT OF THE METALLIZING AGENT,SELECTED FROM THE CLASS CONSISTING OF ALKALI PERBORATES, ALKALICHROMATES, HYDROGEN PEROXIDE, ALKALI PEROXIDES AND NITROBENZENESULFONICACIDS AND THEIR ALKALI SALTS, AND IN THE PRESENCE OF A COMPOUND SELECTEDFORM THE CLASS CONSISTING OF O-, M-, AND P-PHENYLPHENOLS AND THE ALKALIMETAL SALTS THEREOF IN AN AMOUNT RANGING FROM 1% TO 30% BASED ON THEWEIGHT OF THE DYE SOLUTION.